TWI292753B - - Google Patents

Abstract

A method for producing cyclohexanone oxime, which comprises the steps of (1) subjecting to an amination reaction a starting material selected from the group consisting of cyclohexanol, cyclohexanone and a mixture thereof, thereby obtaining cyclohexylamine, and (2) subjecting the obtained cyclohexylamine to a partial oxidation reaction, thereby obtaining cyclohexanone oxime, wherein a by-product (alpha) formed in the step (1) and/or a by-product (beta) formed in the step (2) are/is recycled to a reaction system of the amination reaction in the step (1).

Description

1292753 Α7 Β7 V. Description of Invention (1) [Technical Field of the Invention] (Please read the precautions on the back side and then fill out this page) The present invention relates to a method for producing cyclohexanone oxime. More specifically, the present invention relates to a process comprising the steps of: (1) preparing a cyclohexylamine via amination reaction of a starting material selected from the group consisting of cyclohexanol, cyclohexanone, and mixtures thereof, and 2) a step of subjecting the obtained cyclohexylamine to a cyclohexanone oxime via a partial oxidation reaction, wherein the by-product (α) formed in the step (1) and/or the by-product formed in the step (2) (W), a method for producing cyclohexanone oxime characterized by recycling in the reaction system of the amination reaction of the step (1). According to the content of the present invention, the cyclohexanone oxime which is suitable as an intermediate of ε-caprolactam which is a raw material such as tron-6 can be used without any complicated steps required for the conventional method, and is required for the production. A reagent such as a hydroxylamine salt can be obtained by simply operating at a very high selectivity using only a small amount of hydrogen consumption and a simple device. According to the method of the present invention, the Ministry of Economic Affairs' Intellectual Property Office employee consumption cooperative prints, and does not produce the separation of the quality of the compound ε-caprolactam produced by cyclohexanone oxime which is easily produced by the prior art. By-products such as by-products and/or low industrial price, such as ammonium sulfate, can be reused except for most of the by-products formed. In addition, almost all of the by-products that are not recycled are also useful compounds such as cyclohexane. The waste is extremely small, so it is extremely advantageous for industrial manufacture. [Prior Art] Among the methods for producing cyclohexanone oxime, a method widely used in the industry is to first obtain cyclohexanone by using a reaction step composed of benzene as a starting material in multiple stages, and additionally produce ammonia. The prepared hydroxylamine salt is then applied to the Chinese National Standard (CNS) Α4 specification (210X297 dongdong) -4- 1292753 Α7 Β7 5. Inventive Note (2) Cyclohexanone and Hydroxylamine A method in which a salt is reacted to obtain cyclohexanone oxime. That is, the above method mainly includes the following three reaction steps. (I) A step of preparing cyclohexanone from benzene. (II) A step of additionally preparing a hydroxylamine salt from ammonia in addition to the step (I). (III) A step of preparing cyclohexanone oxime from a hydroxylamine salt and cyclohexanone. The above-mentioned method for producing cyclohexanone in the step (I) ("Chemical Engineering", ν〇1·55, Νο·5, 3 8 2, 1991, Institute of Chemical Engineering, Japan, and "Catalyst", Vol. 33, Ν〇·5,341,1991 Catalyst Society, Japan), the air oxidation of cyclohexane is the mainstream, and some of them are obtained by hydrogenation of phenol. A method for producing cyclohexane oxidation, for example, by completely hydrogenating benzene as cyclohexane, and then oxidizing it by air to obtain a mixture of cyclohexanol and cyclohexanone, and then distilling the cyclohexanol with cyclohexanone. Separation and dehydrogenation of the separated cyclohexanol to produce cyclohexanone. However, this method not only has many steps, but in the air oxidation step of cyclohexane, in order to increase the selectivity without inhibiting the conversion rate to 3 to 10%, the production amount is lowered, and the unreacted ring has been made. Alkane is recycled, and a large amount of energy must be used. The selectivity is only 73~83%, but it cannot reach sorghum. The by-products, for example, form carboxylic acids, alcohols, aldehydes, ketones, ethers, esters, hydrocarbons, etc., and the aforementioned by-products are generally separated from the product and discarded. Among the above-mentioned by-products, water-soluble carboxylic acids and lower alcohols can be removed by water extraction, and water-insoluble carboxylic acids, esters and the like can be removed by saponification in an aqueous alkali solution. Subsequently, most of the residual by-products can be removed by distillation. However, cyclohexanone and cyclohexanol are very similar to the boiling point. For example, the paper size is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297 mm) (please read the notes on the back and fill out this page)

, τ Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1292753 Α7 Β7 V. Invention description (3) Cyclohexyl butyl ether, η-pentyl cyclohexane, cyclohexyl acetic acid, hexahydroxybenzaldehyde, etc. are extremely difficult to remove. The aforementioned by-products are also responsible for the deterioration of the quality of the ε-caprolactam of the desired compound. A variety of methods for separating such by-products are known (Japanese Patent Publication No. Sho 60-39656 (corresponding to U.S. Patent No. 4,661,430), Japanese Patent Application Laid-Open No. Hei No. 5-271-143, Japanese Laid-Open No. 5-30 No. 1858, etc., but the number of separation steps is extremely large and the operation is extremely complicated, so it is not an advantageous method. Further, the air oxidation method of cyclohexane, for example, also increases the conversion rate to 12 to 15% in the presence of boric acid, and the selectivity is increased to about 90%, but it is extremely difficult to carry out the cyclohexane or boric acid slurry. It is processed and it must be recycled, so it is extremely complicated in operation. Further, in the dehydration step of the above cyclohexanol, the conversion of cyclohexanol is limited to about 70 to 90% due to the limitation of the reaction equilibrium, and the boiling point of the cyclohexanol of the starting material and the cyclohexanone of the product is extremely high. Similar, it is often necessary to use a large amount of energy for separation. The method for producing hydrogenated phenol is also the first method used, which is a method in which benzene-derived phenol is hydrogenated by a catalyst such as nickel or palladium to obtain cyclohexanol or cyclohexanone. However, for example, when a method for producing phenol from benzene or the like is carried out by using the cumene method of a representative method, the number of reaction steps is likely to be extremely large, and since it is generally a step of producing acetone, it is also required to be acetone. And the production of phenol is limited due to problems such as price. The representative production method of the hydroxylamine in the above step (II), for example, the RASCHIG method described in the conventional method (Industry Organic Chemistry, 4th edition, Toyama Kosuke, Tokyo Chemicals, 287, 1996) This paper size is applicable _ National Standard (CNS) Α4 Specification (210X297 mm) Please read the back ί Matter Extravagance Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Print -6 - 1292753 A7 B7 V. Invention Description (4 ) ) Mainly consists of a four-stage step. Ammonium nitrite synthesized by a mixture of N 〇 and N 0 2 obtained by oxidizing ammonia, carbon dioxide and hydrogen obtained by the oxidation of ammonia with ammonia is reduced by S02 as a sulfonic acid. An ester which is subsequently hydrolyzed to a sulfate of a hydroxylamine, but which is extremely complicated in addition to the manufacturing steps, and industrially utilizing ammonium sulfate having a very low valence, which is 1 mol per 1 hydroxyl group of hydroxylamine sulfate In this way, under the combined deuteration, a total of 2 moles of ammonium sulfate is generated for the cyclohexanone oxime 1 mole. Further, in the hydroxylamine sulfate method (HSO method) and the hydroxylamine phosphate method (HPO method), although a hydroxylamine salt can be produced and used to produce cyclohexanone oxime, it is associated with the step (III). The foregoing method still has many problems. In the above step (III), the method of sulfonating cyclohexanone using a sulfate of a hydroxylamine is the mainstream of "Industrial Organic Chemistry, 4th Edition, Tokyo Chemical Co., Ltd., page 285, 1996, Japan" method. However, in order to balance the deuteration reaction, a certain amount of ammonia needs to be added to maintain the pH near the reaction. This step also causes the industrial price to be extremely low, and the ammonium sulfate is produced as a by-product to the cyclohexanone oxime formed. 1 Mohr produces 1 mole at the same time. In steps (II) and (III) above, the HSO method (U.S. Patent No. 3,941,83, No. 4,031,139) is based on the presence of ammonia in a platinum catalyst. The NO obtained by oxidation is reduced by hydrogen in the presence of a platinum-based catalyst in an ammonium hydrogen sulfate/ammonium sulfate buffer to form ammonium hydroxyamine sulfate, which is then reacted with cyclohexanone. In addition, the above-mentioned HPO method (U.S. Patent No. 3,948,988, No. 3,940,422) also produces nitrate ions obtained by oxidation of ammonia on a palladium paper scale according to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ( Please read the notes on the back and fill out this page.)

11 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1292753 A7 B7 V. Invention Description (5) (Please read the note on the back and fill out this page) In the presence of catalyst, in phosphate/ammonium phosphate buffer Hydrogen is reduced to form a hydroxyammonium phosphate which is then reacted with cyclohexanone. In either case, since the buffer is circulated between the hydrazine manufacturing step and the hydroxylamine production step, the pH 値 can be kept constant, and there is an advantage that ammonium sulfate does not form by-products, but the number of reaction steps is extremely high and must be high. Since the raw material of purity is easy to generate catalyst recovery or the buffer circulation step is extremely complicated. Further, the selectivity of the hydroxylamine was as low as 60% for ammonium in the entire step. Further, in the method consisting of the above steps (I) to (III), a large amount of hydrogen is often required for the complete hydrogenation of benzene and the production of a hydroxylamine salt, which often causes problems. The Ministry of Economic Affairs, the Intellectual Property Bureau, the employee consumption cooperative, printed it, and also proposed the method for the above. The improved method, for example, in the method for producing cyclohexanone, benzene can be obtained by partial hydrogenation to obtain cyclohexene, and then the cyclohexanol obtained by the hydration reaction can be subjected to dehydrogenation reaction. A method for producing cyclohexanone (Japanese Laid-Open Patent Publication No. Hei 5 6-4 3 227 (corresponding to EP 23 379)) and the like. In the method, compared with the cyclohexane air oxidation method, the hydrogen consumption is small, and the cyclohexanone which is produced by the partial hydrogenation reaction is contained, so that the carbon-based yield substantially approaches 100%. Other advantages, but still have the reaction equipment of the cyclohexanol dehydrogenation step, and the energy cost and the like are relatively large with respect to the air oxidation method. Further, a method of reacting cyclohexanone with ammonia in the presence of hydrogen peroxide to produce cyclohexanone oxime is known (U.S. Patent No. 4,745,221). However, in this method, since it is not necessary to use a reagent obtained by a complicated method such as hydroxylamine, and is a method which does not produce by-products such as ammonium sulfate, it still has the Chinese National Standard (CNS) A4 specification (this is required for the paper scale). 210X297 mm) -8- 1292753 A7 B7 V. INSTRUCTIONS (6) Use high-priced hydrogen peroxide and other problems. (Please read the precautions on the back side and fill out this page.) Also, the method of producing cyclohexanone is not carried out, for example, cyclohexane obtained by completely hydrogenating benzene, and a mixture of NO and N〇2 obtained by air-oxidizing ammonia. The method for producing cyclohexanone oxime hydrochloride by the reaction of sulfuric acid and hydrochloric acid to obtain cyclohexanone oxime hydrochloride (organic synthetic chemistry association, 21, 160-3, 1 963, organic synthetic chemistry association) Japan) has been industrialized. In this method, since cyclohexanone is used as an intermediate material, the reaction step is relatively small. However, since light is required for deuteration, in addition to the large amount of electricity used, the maintenance of mercury lamps and the like is extremely complicated. In addition, the cyclohexane obtained by the complete hydrogenation of benzene is reacted with nitric acid obtained by oxidation of ammonia to obtain nitrocyclohexane, which is then partially hydrogenated to produce cyclohexanone oxime. Methods are also known (U.S. Patent No. 3,255,26, No. 2,967,200). In this method, the oxidation reaction is carried out using nitric acid, and is carried out at a high temperature of about 1 to 50 ° C and a high temperature of about 3 to 4 MPa, and has a problem that a large amount of equipment materials are consumed and the risk of explosion is likely to occur. Moreover, the selectivity of nitrocyclohexane is about 80% lower on the basis of cyclohexane and on the basis of nitric acid, and the conversion of cyclohexane is lower than 15 to 25%, so the productivity is lower. Low, unreacted cyclohexane consumes a lot of energy when recycled. Further, the selectivity of the production step of the partially hydrogenated cyclohexanone oxime of nitrocyclohexane is also only about 80% lower. As described above, the conventional methods for producing cyclohexanone oxime have complicated manufacturing steps, and therefore, in industrial practice, a simpler and more efficient method is sought. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -9- 1292753 Α7 Β7 V. Invention description (7) [Summary of invention] (Please read the note on the back and fill out this page) In this case, the inventors have intensively studied in order to solve the aforementioned problems. As a result, it was found that (1) a step of preparing a cyclohexylamine via amination reaction of a starting material selected from a group consisting of cyclohexanol, cyclohexanone, and a mixture thereof, and (2) a step of producing a cyclohexanone oxime via a partial oxidation reaction of cyclohexylamine, wherein the by-product (α) formed in the step (1) and/or the by-product (cold) formed in the step (2) may be When the cyclohexanone oxime is produced by recycling in the reaction system of the amination reaction, the cyclohexanone oxime can be used without any reaction reagent such as a hydroxylamine salt obtained by using a complicated step. Low hydrogen consumption, simple device, simple operation, can be manufactured at a very high selectivity, and it does not produce the desired intermediate of cyclohexanone oxime produced by the prior art. - by-products of which the quality of caprolactam has adverse effects and are difficult to separate, and/or ammonium sulfate having a lower industrial price, and most of the by-products produced can be recycled, and there are many by-products that are not recycled. Is a useful compound such as cyclohexane, so And very rarely thrown away in favor of industrial use. In the first place of the present invention, one of the objects of the present invention is a cyclohexanone oxime which is a compound which is suitable as an intermediate of ε-caprolactam which is a raw material of Nile-6. It is not necessary to use a reagent such as a hydroxylamine salt obtained by using a complicated step in the past, and it can be manufactured at a very high selectivity without a small amount of hydrogen consumption, a simple device, and a simple operation. The paper produced by the technology has adverse effects on the quality of ε-caprolactam of the desired intermediate prepared by cyclohexanone oxime and is difficult to separate by-products and/or industrial grades. Standard (CNS) Α4 size (210 X 297 mm) -10- 1292753 A 7 B7 V. Description of invention (8) (Please read the note on the back and fill out this page) Ammonium sulfate, and the by-products produced are large Some of them can be recycled, and the by-products that are not recycled are mostly useful compounds such as cyclohexane, so that waste is extremely small and extremely advantageous for industrial use. The other objects, features, and advantages of the invention will be apparent from the description and appended claims. DETAILED DESCRIPTION OF THE INVENTION According to the present invention, a method for producing cyclohexanone oxime is provided, which comprises (1) a selected starting group of cyclohexanol, cyclohexanone and a mixture thereof. a step of preparing a cyclohexylamine by an amination reaction, and (2) a step of subjecting the obtained cyclohexylamine to a cyclohexanone oxime via a partial oxidation reaction, wherein the side formed in the step (1) At least one by-product selected from the group consisting of the product (α) and the by-product (/3) formed in the step (2), can be recycled in the reaction system of the amination reaction of the step (1). A method for producing cyclohexanone oxime. Printed by the Ministry of Economic Affairs, the Intellectual Property Office, and the Consumer Cooperatives. In order to facilitate the understanding of the present invention, the features and preferred embodiments of the present invention are enumerated below. 1. A method for producing cyclohexanone oxime, which comprises (1) preparing a cyclohexylamine by amination reaction of a starting material selected from the group consisting of cyclohexanol, cyclohexanone and a mixture thereof Step, and (2) the step of preparing the cyclohexanone oxime by partial oxidation reaction of the obtained cyclohexylamine, the paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210×297 mm) -11 - 1292753 Α7 Β7 5 , invention description (9) (please read the note on the back and then fill out this page) where the by-product (α) generated in step (1) and the by-product (/3) generated in step (2) At least one by-product selected from the group can be recycled in the reaction system of the amination reaction of the step (1). 2.  The method according to the above item 1, wherein when the cyclohexanol is used as the starting material in the step (1), the by-product (α) comprises at least one selected from the group consisting of cyclohexanone and fluorene-cyclohexylene. a compound in a group of amines, dicyclohexylamine, cyclohexylaniline and aniline; when cyclohexanone is used as a starting material in the step (1), the by-product (containing at least one selected from cyclohexanol and hydrazine) a compound in the group of (cyclohexylene)cyclohexylamine, dicyclohexylamine, cyclohexylaniline and aniline; when a mixture comprising cyclohexanol and cyclohexanone is used as the starting material in step (1), The by-product (α) comprises at least one compound selected from the group consisting of cyclohexanol, cyclohexanone, fluorene-(cyclohexyl)cyclohexylamine, dicyclohexylamine, cyclohexylaniline and aniline; The by-product (/3) comprises at least one compound selected from the group consisting of cyclohexanone, nitrocyclohexane, fluorene-(cyclohexylene)cyclohexylamine, and dicyclohexylamine. Intellectual Property Bureau employee consumption cooperative printed 3.  The method according to the above item 1, wherein the amination reaction in the step (1) is carried out by containing at least one element selected from the group consisting of Groups 8, 9 and 10 of the periodic table, chromium, copper, silver, zinc and aluminum. Performing in the presence of an aminated catalyst of the elements in the group. 4. The method according to the above item 3, wherein the amination reaction in the step (1) is carried out in the presence of a molecular hydrogen. 5. The method according to the above item 1, wherein the partial oxidation of the paper in the step (2) is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297 mm) -12-1262953 A7 B7 5. The invention description (10) should It is carried out in the presence of molecular oxygen as an oxidizing agent. 6. The method according to the above item 1, wherein the cyclohexanol is obtained by a method comprising: (i) partially hydrogenating benzene to obtain cyclohexene, (ii) hydrating the obtained cyclohexene, and the like. . 7.  The method of the above item 6, wherein the partial hydrogenation of the benzene is carried out in a hydrogenation catalyst containing at least one element selected from the group consisting of elements belonging to Groups 8, 9 and 10 of the periodic table, in the presence of water Conductor. 8.  The method according to the above item 6, wherein the partial hydrogenation reaction of the benzene is carried out in (a) a metal ruthenium having an average crystal grain size of 200 A or less, and, if necessary, a hydrogenation catalyst containing a zinc compound, (b) water, and (c) Providing at least one compound selected from the group consisting of chromium or an oxide thereof, a water-soluble zinc compound, and a solid alkaline zinc sulfate in a neutral or acidic condition, and the hydrogenation catalyst is Non-loaded. 9.  The method according to the above item 6, wherein the hydration reaction of the cyclohexene is carried out in the presence of a hydrated catalyst of zeolite. 10.  The method of item 9, wherein the zeolite is selected from the group consisting of ZSM-5 type zeolites. 11.  The method according to the above item 1, wherein the cyclohexanone comprises (i) partially hydrogenating benzene to produce cyclohexene, (ii) hydrating the obtained cyclohexene to produce cyclohexanol, (iii) A method obtained by subjecting the obtained cyclohexanol to dehydrogenation treatment or the like. 12.  The method according to the above item 11, wherein the partial hydrogenation reaction of the benzene is carried out in a hydrogenation catalyst containing at least one element selected from the group consisting of elements belonging to Groups 8, 9 and 10 of the periodic table, in the presence of water The person who performed it. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) (please read the notes on the back and fill out this page). • Installation 智慧 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed - 13- 1292753 Α7 Β7 V. Description of invention (11) (Please read the notes on the back and fill in this page) 1 3. The method according to the above item 11, wherein the partial hydrogenation reaction of the benzene is carried out in (a) a metal ruthenium having an average crystal grain size of 200 A or less, and, if necessary, a hydrogenation catalyst containing a zinc compound, (b) water, and (c) Providing at least one compound selected from the group consisting of chromium or an oxide thereof, a water-soluble zinc compound, and a solid alkaline zinc sulfate in a neutral or acidic condition, and The media is not loaded. 14. The method according to the above item 11, wherein the hydration reaction of the cyclohexene is carried out in the presence of a hydration catalyst of zeolite. The method of item 11, wherein the zeolite is selected from the group consisting of ZSM-5 type zeolites. Hereinafter, the present invention will be described in more detail. The Ministry of Economic Affairs Intellectual Property Office employee consumption cooperative prints the step (1) of the present invention, wherein a starting material selected from the group consisting of cyclohexanol, cyclohexanone and a mixture thereof is subjected to an amination reaction to obtain a ring. Hexylamine. The amination reaction is carried out in the presence of ammonia, preferably in the presence of ammonia and molecular hydrogen, using a catalyst. Specifically, for example, the method described in the publicly known literature can be used. For example, when cyclohexanol is used as a raw material, a method of reacting in the gas phase using copper oxide-zinc oxide as a catalyst in the presence of ammonia and hydrogen ("Journal of Industrial Chemistry", 70 (9), 1 508, 1967, Japan Chemical Society, Japan), in the presence of ammonia and hydrogen, a method of reducing a nickel forming catalyst in a gaseous form using a diatomaceous earth carrier to carry out a reaction under normal pressure (Japanese Patent Publication No. 51-41627) In the presence of ammonia and hydrogen, the method of using a catalyst containing a main component in the liquid phase based on conditions such as temperature and pressure (Japanese Patent Publication No. 5 1 -3260 No. 1) Method for amination of an alicyclic alcohol in the presence of a ruthenium catalyst obtained by hydrogen pretreatment (this paper scale is suitable for households (CNS) Α4 specification (21GX297 mm). Painting - 14 - 1292753 A7 B7 V. Invention (12) 曰本特开平5-148191号). When cyclohexanone is used as a starting material, a method of reacting with a catalyst such as nickel, cobalt, platinum, or palladium in the presence of ammonia and hydrogen (Chemical Abstract, 15, 1 285, 192 1 ) 'in ammonia and hydrogen In the presence of a nickel catalyst, it is reacted in a liquid phase ("Journal of Industrial Chemistry", 70 (8), 1 335, 1967, Japanese Chemical Society 'Japan'). Further, when a mixture of cyclohexanol and cyclohexanone is used as a starting material, a method in which a nickel oxide-oxidizing catalyst is used in a gas phase in the presence of ammonia and hydrogen is used (French Patent No. 1,492,098) The specification is a method of reacting nickel and/or cobalt with phosphoric acid or boric acid in a gas phase in the presence of ammonia and hydrogen (Japanese Patent Publication No. Sho 41-7575). The catalyst used in the present invention may be any metal, metal oxide, metal salt, or organometallic compound, etc., but contains at least one element selected from Groups 8, 9 and 10 of the periodic table (Fe, Co). , Ni, Ru, Rh, Pd, Ir, Pt, etc.), a catalyst of a metal element in the group of Cr, Cu, Ag, Zn and A1 is preferred. The catalyst may be in the form of a metal or metal oxide, or a metal or metal oxide supported by a suitable catalyst carrier. The catalyst carrier is, for example, activated carbon, Si〇2, Ah〇3, Si〇2/Al2〇3, Ti〇2, Zr〇2, Zn〇, barium sulfate, potassium carbonate, diatomaceous earth, zeolite or the like. The amination reaction of the present invention can be carried out in a continuous or batch form in a fixed bed or a suspended bed in a gas phase or a liquid phase. When the reaction is carried out in a liquid phase, the reaction may be carried out in the presence of a solvent. The solvent is not particularly limited. For example, a nitrile such as acetonitrile or propionitrile can be used. 'N-hexane, cyclohexane. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210Χ297 mm) 丨^---„- ---V·装—(Please read the note on the back and fill out this page) Order the Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Print -15- 1292753 A7 __ B7 V. Invention Description (13) (Please read the back first Note: Please fill in this page) Aliphatic hydrocarbons, aromatic compounds such as benzene and toluene, ethers such as dioxane and diether, water, etc. When operating under a solvent, the concentration of cyclohexanol is generally It is 1 to 30% by weight, preferably 5 to 20% by weight. Further, the same reaction may be carried out in the reaction in the gas phase, and it is only necessary to vaporize the solvent before supplying it to the reactor. In the case of cyclohexanol and/or cyclohexanone, the molar ratio of ammonia is generally 0. 5/1 to 10/1, preferably in a ratio of 1/1 to 5/1, and in the case of performing an amination reaction in the presence of molecular hydrogen, for cyclohexanol and/or cyclohexanone In other words, the molar ratio of hydrogen is generally 0. 01/1 to 10/1, preferably 0. The ratio of 5/1 to 5/1 is generally 0 when it is carried out under pressure. The range of 1 to 20 MPa, preferably 1 to 10 MPa, is preferably 50 to 300 ° C, preferably 80 to 250 ° C. The reaction time can be set according to the target selection rate or yield of the target alicyclic hexanol ammonia, and only needs to be appropriately selected without particular limitation, and is usually from several seconds to several hours. The amount of catalysts printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs varies generally depending on the type of catalyst used. As long as the amount of expected effect is achieved, there is no particular limitation. For the substance (cyclohexanol and / or cyclohexanone), by weight ratio of 0. 0001/1 ~ 100/1, preferably 0. Range of 001/1 ~ 50/1. Further, when the reaction is carried out in the gas phase, the liquid hourly space velocity (LHSV) in the upflow or downflow reactor is preferably 0. 01~10, more preferably 0. It is preferable to carry out the reaction under the conditions of 05 to 5 and the like. The by-product (α) of the amination reaction in the step (1) differs depending on the starting materials, catalysts, etc. used. Generally, the step (1) is based on the Chinese National Standard (CNS). Α4 specification (210 X 297 mm) A-16- 1292753 A7 B7_ _ V. Invention description (14) (Please read the back note and then fill out this page)) When using the starting material in cyclohexanol, The by-product (^) comprises at least one compound selected from the group consisting of cyclohexanone, fluorene-(cyclohexyl)cyclohexylamine, dicyclohexylamine, cyclohexylaniline and aniline; in step (1) When the starting material uses cyclohexanone, the by-product (α) comprises at least one selected from the group consisting of cyclohexanol, cyclohexanone, fluorene-cyclohexylamine cyclohexylamine, dicyclohexylamine, cyclohexyl. a compound in the group consisting of aniline and aniline; when a mixture comprising cyclohexanol and cyclohexanone is used as the starting material in the step (1), the by-product (α) comprises at least one selected from the group consisting of cyclohexanol and a ring. Compounds in the group of ketone, fluorene-(cyclohexylene)cyclohexylamine, dicyclohexylamine, cyclohexylaniline and aniline The Huishang Bureau employee consumption cooperative is printed on the produced cyclohexylamine, for example, the reaction mixture in a reactor separated by a catalyst, added with cyclohexane or benzene, etc., after azeotropic distillation, and recovered by distillation separation. If necessary, the separation step can be used to achieve the desired purity. Further, the cyclohexylamine formed and the by-product (α) can be supplied to the partial oxidation reaction of the step (2) without being separated. The by-product (/3) can be recycled to the step (1). The purity of the partial oxidation reaction of the cyclohexylamine in the step (2) is preferably 80% or more, more preferably 95%, and 99. The above is the best. The method of partially oxidizing the cyclohexylamine of the step (2) of the present invention to obtain cyclohexanone oxime, for example, a method in which cyclohexylamine is reacted with an oxidizing agent in the presence of a catalyst, and the like. The oxidizing agent of the present invention may be an oxygen such as molecular oxygen or ozone, an inorganic hydroperoxide such as hydrogen peroxide, peracetic acid or K2S2〇8, t-butyl hydroperoxide or cumene hydroperoxide. Organic hydrogen such as ethylbenzene hydroperoxide and cyclohexyl hydroperoxide Oxide, NaCIO, NaBrO, this paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -17- 1292753 A7 B7 V. Invention description (16) (Please read the note on the back and fill out this page) The partial oxidation reaction of the present invention can be carried out in a continuous or batch manner in a fixed bed or a suspended bed in a gas phase or a liquid phase. When carried out in a liquid phase, the reaction can be carried out in the presence of a solvent. There is no particular requirement for the solvent, for example, the solvent described in the above-mentioned well-known technique (Japanese Patent Laid-Open No. Hei 2-295956 (corresponding to EP 395046), U.S. Patent No. 2,706,204), for example, methanol, t-butanol Such as C1 to C10 alcohol, acetonitrile, benzene, toluene, dimethylformamide, dimethylsulfonate, triethylamine, dimethoxyethane, dioxane, diether, water, and the like. When the operation is carried out in the presence of a solvent, the concentration of cyclohexylamine is usually from 1 to 30% by weight, preferably from 5 to 20% by weight. When the reaction is carried out in the gas phase, the concentration of the supplied cyclohexylamine is preferably 0. 5 to 20%, more preferably 2 to 10%. The cyclohexylamine may be supplied to the reactor alone, or may be diluted with an inert gas such as nitrogen or helium which does not affect the reaction. Further, the above solvent may be vaporized before being supplied to the reactor. The Ministry of Economic Affairs' Intellectual Property Office staff consumption cooperative prints the reaction conditions. For example, it can be appropriately selected according to the type of oxidant or catalyst used. The reaction pressure can be reduced pressure, normal pressure or pressure. The total pressure is not particularly limited. The reaction temperature is preferably from 20 ° C to 300 ° C, more preferably from 80 ° C to 250 ° C. When the reaction temperature is higher than 300 °C, the resulting cyclohexanone oxime tends to promote decomposition or peroxidation, and when the reaction temperature is lower than 20 °C, the reaction rate tends to decrease. Further, the reaction time can be determined according to the target selectivity of cyclohexanone oxime or the target of the yield, and it can be appropriately selected, and it is not particularly limited, and is usually from several seconds to several hours. This paper scale applies to the 81 national standard (CNS) A4 specification (210X297 mm) -19- 1292753 A7 __ B7 V. Invention description (17) (Please read the back note before completing this page) About the use of catalyst The amount is different depending on the type of the catalyst to be used. Generally, as long as the desired catalyst effect can be achieved, it is not particularly limited. Generally, for cyclohexylamine, the weight ratio is 0. 0001/1 to 100/1, preferably 0. Range of 001/1 to 50/1. Further, when the reaction is carried out in the gas phase, the liquid hourly space velocity (LHSV) in the upflow or downflow reactor is preferably 0. 01~10, more preferably 0. It is preferable to carry out the reaction under the conditions of 05 to 5 and the like. The by-product (yS) formed in the partial oxidation reaction in the step (2) generally comprises at least one selected from the group consisting of cyclohexanone, nitrocyclohexane, N-(cyclohexyl)cyclohexylamine and bicyclic ring. a compound in the group of hexylamine. The resulting cyclohexanone oxime can be recovered by a conventional method such as distillation or extraction from the reaction mixture in the reactor from which the catalyst is separated, and if necessary, can be passed through a separation step to attain the desired purity. In this case, the purity of the cyclohexanone oxime is preferably 99% or more. In the present invention, the by-product (α) generated in the step (1) and/or the by-product (/3) generated in the step (2) can be recycled to the present invention. The reaction of the amination reaction in the step (1) is carried out to be converted into cyclohexylamine. That is, the by-product is equivalent to a cyclohexylamine or the like which is a raw material for supplying an amination reaction or an intermediate product for producing a cyclohexanone, and based on the recycling of the by-product, the cyclohexanone oxime of the target product can be further raised. Choice rate. Further, the by-product (^) generated in the step (1) may be the same compound as the by-product (泠) produced in the step (2), in this case, by-product (α) and by-product (/). 3) Both can be recycled in step (1) at the same time, or only one paper scale is applicable to China National Standard (CNS) Α4 specification (210Χ297 mm) -20- 1292753 A 7 B7 V. Invention description (18) It can be recycled in step (1). For example, when the by-product (α) and the by-product (0) are simultaneously dicyclohexylamine, the by-product (α) of dicyclohexylamine is recycled together with the by-product (n) dicyclohexylamine to the step (1). , or either side can be recycled to step (1) for reuse. In the amination reaction of the starting material with the by-product, the conversion reaction of cyclohexylamine can be carried out by the following reaction formula (cyclohexanol (I), cyclohexanone (oxime), nitrocyclohexane (ΠΙ), The reaction is carried out in the form of dicyclohexylamine (IV), fluorene-cyclohexylcyclohexylamine (V or VI), cyclohexylaniline (VII), and aniline (VIII). (I) C6HuOH + NH3^ C6H11NH2 + H2O; (II) C6HlO + NH3 + H2-^ C6H11NH2 + H2O; (III) C6HuN〇2 + 3H2^ C6H11NH2 + 2H2O; (IV) C6Hu-NH-C6Hu + NH3^ 2C6H11NH2 (V) C6Hl〇= N-C6Hll + H2 + NH3->2C6H11NH2; (VI) C6Hl0 = N-C6Hll + H2〇-> C6H11NH2 + C6H10O; (VII) + and (VIII) C6H5NH2 + 3H2-&gt (:6ΗηΝΗ2. The by-product (^) formed by the amination reaction in the step (1), and/or the separation and recycling of the by-product (/5) formed by the partial oxidation reaction in the step (2), etc. Specifically, for example, it can be carried out by the following method. First, the separation and recycling of the by-product (^) will be described. When the by-product (α) contains two or more kinds of the above-mentioned compounds, it is generally As long as at least one compound is separated and recycled, 'but the compound of the by-product (^) is completely separated and recycled. The user's national standard (CNS) Α4 specification (210X297 mm) is the most applicable paper scale. (Please read the notes on the back and fill out this page) • 1 Pack · Book the Ministry of Economic Affairs Intellectual Property Bureau staff consumption Printing by the Society-21 - 1292753 A7 B7 V. Description of Invention (19) (Please read the notes on the back and fill out this page.) Good. The specific method of separation and recycling, for example, the reaction mixture obtained by amination reaction In the residue obtained by separating cyclohexylamine by distillation or the like, a component which does not adversely affect the amination reaction of the step (1) (for example, a tar-like high boiling point compound) is removed by a known separation method such as distillation or extraction. Thereafter, the method used in the amination reaction of the step (1), and the residue obtained by separating the cyclohexylamine by distillation or the like, and at least one of the by-products (α) are known as distillation, extraction, and the like. The separation method is separated, recycled to the recycling method used in the amination reaction of the step (1), etc. Further, in the amination step, the produced water may be recycled together with by-products or separated from by-products. The Ministry of Economic Affairs, the Intellectual Property Office, and the Consumer Cooperatives, will print out the steps of separation and recycling of by-products (/3). By-products (/3) generally contain more than two kinds. Generally, at least one compound may be separated and recycled, but it is preferred to separate and recycle the by-product (Θ) compound. The specific method of separation and recycling, for example, In the residue obtained by the partial oxidation reaction, the residue obtained by separating the cyclohexylamine by distillation or the like, the component which does not adversely affect the amination reaction of the step (1) (for example, a tar-like high boiling point compound) is distilled and extracted. After removal by a known separation method, the method of recycling to the amination reaction of the step (1), and the residue obtained by separating the cyclohexylamine by distillation or the like, at least one by-product (/5) of the compound The separation is carried out by a known separation method such as distillation or extraction, and recycled to the recycling method used in the amination reaction of the step (1). Further, in the amination step, the produced water may be recycled together with the by-product or may be separated from the by-product. This paper scale applies to China National Standard (CNS) A4 specification (210x297 mm) 1292753 A7 __B7 V. Invention description (20) 4 (Please read the note on the back and fill in this page) Again, the amino group of step (1) In the reaction, when the unreacted starting material (cyclohexanol and/or cyclohexanone), ammonia, and, if necessary, hydrogen, the reaction system for recycling it to the amination reaction of the step (1) is preferred. . In this case, the above-mentioned unreacted reaction may be carried out separately or recycled together with by-products (α) and/or by-products (,). Further, in the partial oxidation reaction of the step (2), when the unreacted cyclohexylamine and oxygen are present, the partial oxidation reaction system which is recycled to the step (2) is preferably a by-product (α) and (/3). It may be recycled to the amination reaction system of the step (1), respectively, or may be recycled after mixing. Further, in either of the step (1) or the step (2), it is also possible that the recyclable by-product is not produced in the step (1), and at this time, either of the step (1) or the step (2) The recyclable by-product produced (byproduct (α) or by-product (yS)) must be recycled to step (1). In the amination step of the present invention (1), in the amination step of the present invention (1), the cyclohexanol and/or cyclohexanone used as the starting material can be used as described above. It is preferably obtained by subjecting cyclohexene obtained by partial hydrogenation of benzene to cyclohexanol obtained by hydration treatment, and/or cyclohexanone obtained by dehydrogenating cyclohexanol obtained by the method. . In the case of using cyclohexanol and/or cyclohexanone to produce cyclohexanone oxime, the total carbon recovery of useful materials (including cyclohexane) from the benzene of the starting material to the cyclohexanone oxime of the target product It is far superior to other methods. Further, this method also has the advantage of producing cyclohexanone oxime using a small amount of water consumption, and it is difficult to produce by-products which are difficult to separate. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -23- 1292753 A7 B7 V. Invention description (21) (Please read the note on the back and fill in this page) The following 'will be the benzene part The method of hydrogenating to produce cyclohexene is described in the same manner as the method of producing cyclohexanol by hydration with cyclohexene. Further, the method for obtaining cyclohexanone by dehydrogenation of cyclohexanol obtained by this method can be treated by a conventional dehydrogenation method or the like. The partial hydrogenation of benzene can be carried out by a known method. A known method is, for example, the use of water and an alkali metal and a method comprising at least one catalyst composition selected from the elements of Groups 9 and 10 of the Consumers' Cooperatives of the Intellectual Property Office of the Ministry of Economic Affairs, No. 8 of the Periodic Table of the Year (Japanese Special Public Show 5) No. 6-22850 (corresponding to No. 3,376,720 in the United States)), a catalyst supported on nickel, methane, chromium, titanium or niobium oxide, using alcohol or ester as an additive (Japanese Patent Publication No. 52-3933) a method of reacting in the presence of a neutral or acidic aqueous solution containing at least one salt of a metal belonging to Group 1 and Group 2 metals and manganese in the periodic table containing a ruthenium catalyst (Japanese special) Japanese Laid-Open Patent Publication No. Hei 57-7607 (corresponding to U.S. Patent No. 4,055,51, 2), in the presence of oxides such as cerium oxide and aluminum oxide, supported by a catalyst of cerium, water and cobalt sulfate. A method of partially hydrogenating (Japanese Unexamined Patent Application Publication No. Hei No. Hei No. Hei No. Hei No. Hei. Containing at least one selected from the group consisting of lithium, cobalt, and iron A method of reacting with a metal sulfate in a group of zinc and water (Japanese Patent Publication No. 2-5 9 1 1 (U.S. Patent No. 4,575,572, and EP 1 7 09 1 5) a method in which at least one oxide selected from the group consisting of ceria, titania, and alumina is coexisted in a reaction system in the presence of barium sulfate as a carrier and a supported catalyst and water (Japanese special) Fair 6-4545 (US Patent No. 4,665,274, and EP2 14530 This paper scale applies Chinese National Standard (CNS) A4 Specification (210X297 mm) -24-1292753 A7 B7 V. Invention Description (22) (Please Read the note on the back and fill in the page))). Using hydrogen as a catalyst, use a metal ruthenium crystal having an average particle diameter of 200 A or less and/or its agglomerated particles in water and at least one zinc compound. a method of carrying out a reaction (JP-A-2-19098), in the presence of water and at least one aqueous zinc compound, when hydrogen is partially reduced in a liquid phase under acidic conditions, the hydrogenation catalyst may be Zinc-containing compound For the ruthenium obtained by the reduction of the ruthenium compound, the zinc content is 0. 1 to 50% by weight of a non-supporting catalyst having an average crystal grain size of 200 A or less (曰本特公平2-16736), or a metal having a crystal grain size of 200 A or less in the presence of water a hydrogenation catalyst particle containing a catalyst as a main component, and adding at least one selected from the group consisting of an oxidation pin and an oxidation, which is different from the catalyst, and then coexisting with at least one solid alkaline zinc sulfate A method of carrying out a reaction under neutral or acidic conditions (Japanese Patent Publication No. 3-537-1 (U.S. Patent No. 4,737,536, the disclosure of which is incorporated herein by reference). The Ministry of Economic Affairs, the Intellectual Property Office, and the Staff Consumer Cooperative, which prints a catalyst for partial hydrogenation of benzene, preferably using a hydrogenation catalyst containing at least one metal selected from Groups 8, 9 and 10 of the periodic table. The best metal for the catalyst is 钌. Raw materials for the catalyst, such as halides, nitrates, hydroxides, complex compounds, alkoxides, and the like. Further, the catalyst may contain other metal components as a secondary catalyst in advance. The auxiliary catalyst components such as chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, antimony, gold, etc. are more effective, and zinc is the best. When a secondary catalyst metal is used, the atomic ratio of the auxiliary medium metal is generally 0. 01~20, preferably 0. 1 to 10. The hydrogenation catalyst used may be, for example, a single-element metal oxide such as cerium oxide, aluminum oxide, cerium oxide or titanium oxide or a composite metal oxide thereof. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210×297 mm). ) -25- 1292753 A7 B7 V. INSTRUCTIONS (23) (Please read the notes on the back and fill out this page) Loaded or unsupported type of barium sulfate, calcium carbonate, diatomaceous earth, zeolite, activated carbon, etc. . From the viewpoint of increasing the selectivity of cyclohexene, it is preferred to use a non-supported metal ruthenium. The unsupported metal ruthenium is obtained by reducing the ruthenium compound to a metal state by reducing the ruthenium compound in a gas phase or a liquid phase with hydrogen or a suitable chemical reducing agent. The smaller the average particle diameter of the reduced product, the more advantageous it is for the formation of cyclohexene, and it is preferred to use a metal ruthenium of 200 A or less, more preferably 100 A or less, which is preferable because it can increase the selectivity of cyclohexene. . Among them, the average particle diameter can be a general method, that is, the obtained diffraction ray can be enlarged by the X-ray diffraction method, and calculated by Scherrer's calculation formula. Further, in the present invention, it is also applicable to a metal ruthenium containing a zinc compound which is obtained by the same method. The amount of catalyst varies depending on the type of catalyst used. Generally, for benzene, the weight ratio is 0. 0001/1 to 100/1, preferably 0. Range of 001/1 to 50/1. In the hydrogenation catalyst, when the non-supported metal ruthenium catalyst is used, the chrome and/or the oxide added to the catalyst may be used for the reaction. . The amount of oxide added is lx 1 (Τ3 ～0.) for the water coexisting in the reaction system. 3 times, preferably lx 10_2~0. 1 times. The addition of the above oxide is extremely effective for its effect, which can increase the selectivity and yield of cyclohexene, and can also inhibit the adhesion of the hydrogenation catalyst to the surface of the reactor or the agglomeration of the hydrogenation catalyst. The partial hydrogenation of the benzene must be carried out in the presence of water. The amount of water added is preferably such that the organic phase containing benzene and the cyclohexene formed as the main component and the aqueous phase forming the aqueous phase are formed under the reaction conditions, and the paper scale is applicable to the Chinese national standard. (CNS) A4 size (210X297 mm) -26- 1292753 A7 B7 V. Invention description (24) Therefore, it coexists with 0. 001~1〇〇% by weight, preferably 0. 5 to 20% by weight is preferred. (Please read the precautions on the back side and fill out this page.) Further, in the present invention, it is preferred to carry out the reaction in the presence of a hydrogenation catalyst or water and at least one other water-soluble metal compound. Wherein the water-soluble metal compound is used as an acetate, a chloride, a nitrate, a sulfate, or a phosphate which is an element belonging to Groups 1, 2 and 12 of the periodic table, chromium, lanthanum, iron, cobalt, nickel, copper, or the like. Etc., and metals and zinc chlorides or sulfates of Groups 1 and 2 of the periodic table are preferred, and strong acid salts such as zinc sulfate are more preferred. The zinc sulfate is used in an aqueous solution of 0. 01% by weight to the concentration of saturated solubility is preferred, and more preferably 0. 1 to 30% by weight is more preferred. Further, in the partial hydrogenation reaction of benzene, it is preferred to use a solid alkali sulfate of the above-mentioned metal. at this time. It is more preferable to use solid alkaline zinc sulfate. The solid alkaline zinc sulfate is, for example, ZnS〇4-mZn〇-nH2〇 or ZnS〇4-nZn(〇H) 2 (where m and η are respectively 0. 5Sm$4,0$η S 8 number,), and as Ζη ( 1 +1 ) ( OH) 2 1 —S〇4 (of which, 1 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed as 1 S 1 S 4 a compound of the formula, specifically, for example, ZnS〇4_0. 5Zn〇, ZnS〇4-0. 5Zn〇-H2〇(ZnS〇4-Zn(〇H) 2) or Zn(OH) 2 S〇4, ZnS〇4-3 Zn〇,

ZnS〇4- 3Zn〇-3H2〇(ZnS〇4-3Zn(〇H) 2),

ZnS〇4-3Zn〇-6H2〇, ZnS〇4-3Zn〇-7H2〇, 3Zn〇-8H2〇, ZnS〇c4Zn〇-4H2〇(ZnS〇4-4Zn(〇H ) 2 ), etc. For example, "Inorganic Chemistry", VIII-1, 500, Nine Good, Japan) also contain many compounds. The above-mentioned basic zinc sulfate is known from ancient times, and can be applied to various Chinese paper standards (CNS) A4 specifications (210x297 mm) -27-1292753 A7 _ B7 5. Invention description (25) ( Please read the precautions on the back and fill out this page. The method is generally made by using zinc sulfate as the mother liquor, then reacting it with a suitable base and heating it. Further, the aqueous sulfuric acid solution may be heated in a zinc sulfate aqueous solution by adding zinc hydroxide to obtain various alkaline zinc sulfate mixtures. The above-mentioned elements of Groups 1, 2 and 12 of the periodic table, such as complex, violent, iron, station, nickel, copper and the like, can also be obtained in the same manner. Since the solid alkaline zinc sulfate has a low solubility in water, it can coexist in the reaction system in a solid form only with a small amount of addition. In the present invention, the hydrogenation catalyst is reacted in such a manner that zinc is present in an amount of lx 10 · 4 to 1 by weight, preferably 1 × 1 〇 5 times by weight. Further, the reaction of the partial hydrogenation reaction of benzene is preferably carried out in the presence of a zinc sulfate aqueous solution and/or a solid basic zinc sulfate. It also differs depending on the amount of the zinc compound present, but the reactivity is preferably in a state of being slightly alkaline to acidic. It is preferably carried out in a neutral to acidic state. Specifically, it is better to carry out the reaction under PH1~7, and the PH4~7 or less is more preferable. The partial hydrogenation reaction of the invention is printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative, and generally the liquid phase suspension method can be used. It can be carried out continuously or in batches, or it can be carried out in a fixed bed. The reaction conditions may be appropriately selected depending on the kind or amount of the catalyst or the additive to be used. Generally, the hydrogen pressure is in the range of 0.1 to 20 MPa, preferably 1 to 10 MPa, and the reaction temperature is preferably from room temperature to 250 ° C. It is in the range of 1〇〇~200°C. Further, the reaction time may be set according to the selectivity or yield of the cyclohexene, and may be appropriately selected, and it is not particularly limited, and is usually between several seconds and several hours. That is, in the present invention, the partial hydrogenation of benzene is based on (a) the average crystal grain size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -28-1292753 A7 B7 V. Invention Description (26) a metal ruthenium of 200 A or less, and if necessary, a hydrogenation catalyst containing a zinc compound, (b) water, and (c) at least one selected from the group consisting of chromium or an oxide thereof, a water-soluble zinc compound, and a solid alkaline zinc sulfate Preferably, the presence of the compound in the group is carried out under neutral or acidic conditions, and the hydrogenation catalyst is more preferably carried out under non-loading behavior. The partial hydrogenation reaction of benzene is generally carried out in a four-phase system comprising an aqueous phase containing water, a solid phase containing a catalyst present in the aqueous phase, an oil phase containing a raw material and a product, and a hydrogen-containing gas phase. Or the reaction is carried out in a suspended state. After the partial hydrogenation reaction, the aqueous phase containing the catalyst of the reaction liquid is phase-separated from the produced cyclohexene with an oil phase containing unreacted benzene or the like, and is subjected to an oil phase separation step. The aqueous phase containing the catalyst can be recycled to the reactor in the form of a catalyst slurry for reuse. This partial hydrogenation reaction is generally carried out from cyclohexane, a by-product of the cyclohexene of the product. The separated oil phase contains cyclohexene, cyclohexane and benzene, and since they are in close proximity to each other, they are usually separated by extraction distillation or azeotropic distillation. The isolated cyclohexene can be purified to the necessary purity according to its necessity and in accordance with a general separation step. In this case, the purity of cyclohexene is preferably 99% or more. Generally, the separated unreacted benzene is preferably recycled to the reactor for use. The hydration reaction of cyclohexene can be carried out by a known method. A known method, for example, a method of performing a cyclohexene hydration reaction using a mineral acid, particularly sulfuric acid (Japanese Patent Publication No. Sho 48-447), and a method using an aromatic sulfonic acid (Japanese Patent Publication No. Sho 43-81 04) Japanese Patent Publication No. 43-161 (corresponding to DE 1 230793), a method using a heteropoly acid such as phosphotungstic acid or phosphomolybdic acid (JP-A-53-9746), using ion exchange Resin paper size applies to China National Standard (CNS) A4 specification (210X297 mm 1 ~" one -29 - (please read the back note first and then fill out this page) • Ί.. Ministry of Economic Affairs Intellectual Property Bureau staff consumption Co-operatives printed 1292753 A7 B7 V. Inventions (27) (Please read the note on the back and fill out this page) (Japanese Patent Publication No. 38_15619, JP-A-44_26656) "Molybdenum after de-alkali, A hydration method of an olefin such as a butyl bromide or a zeolite (Japanese Patent Publication No. Sho 47-45323), a method using a crystalline amine-based sand compound ZSM-5 (JP-A-58-194828), etc. Hexene hydration reaction The catalyst used in the present invention is applicable to the catalyst used in the above-mentioned known technical methods, but it is preferably a zeolite catalyst. The zeolite catalyst is generally not used as a catalyst. There are particular limitations, for example, alumina silicates, complex cleavage salts, cerium oxides, alumina phosphates, metal phosphates and their modified zeolites formed by various structures (acid treatment, heat treatment, Dealuminization treatment, etc., in addition, the above zeolite may generally be a proton exchange type (H type), or a part thereof may be an alkali metal such as oils Na, K, Li, etc., an alkaline earth metal such as Mg, Ca, Sr, La The exchange of cation species selected by rare earth metals such as Ce can also be obtained. The Ministry of Economic Affairs, Intellectual Property Bureau, and the Consumer Cooperatives, the best-selling zeolite catalyst is selected from the ZSM-5 zeolite group of crystalline alumina bismuth. Zeolite (hereinafter referred to as "ZSM-5"). The crystalline alumina hydrate ZSM-5 used in the present invention is a zeolite developed by Mobi Petroleum Co., Ltd. (U.S. Patent No. 3,702,886). This ZSM-5 in The molar ratio of Si〇2 and Al2〇3 constituting the crystal is generally 20 or more, and the specific structure of the stereoscopic pore structure having the oxygen 10圜 ring inlet in the crystal structure. In the present invention, the crystalline alumina telluride The cation in ZSM-5 is preferably an alkaline earth metal such as proton, Mg, Ca or Sr, or a rare earth metal such as La or Ce, and the best one is a proton type. The above hydration reaction can be carried out using cyclohexene and water. Or it may be carried out in conjunction with other Chinese paper standards (CNS) A4 size (210X297 mm) 1292753 A7 B7 5. Invention description (28) Machine solvent. In this case, the organic solvent is, for example, a halogenated hydrocarbon, an alcohol 'ether, a ketone or the like. Halogenated hydrocarbons such as dichloromethane, chloroform, tetrachloroethylene, trichloroethane, tetrachloroethane and their corresponding bromides, iodides, fluorides and the like. The alcohol is, for example, an alcohol such as methanol, ethanol, isopropanol, η-propanol or isobutanol 'η-butanol, such as Cl~Cl(). Ethers such as dioxane, tetrahydrofuran, diethyl ether, diisopropyl ether, dipentyl ether, ethylene glycol, dimethyl ether of diethylene glycol or, for example, dipropyl master, cyclobutyl , such as dimethyl sulfoxide and other monoethers and condensed ethers. Ketones such as acetone, methyl ethyl ketone and the like. Any of the above solvents may be used, and a mixture of two or more kinds may be used. In the above hydration reaction, the amount of water used is preferably from 1 to 100 moles per mole of cyclohexene. The amount of the catalyst used is in the range of 0.01 to 100 by weight of cyclohexene. When an organic solvent is used, the cyclopentene capacity ratio is in the range of 0.1 to 100. The reaction temperature in the hydration reaction is generally from 50 to 300 ° C, preferably from 100 to 200 ° C. The reaction pressure can be carried out in any of a reduced pressure, a normal pressure, and a pressurization, and it is more preferably carried out under pressure. The reaction time can be substantially set according to the selectivity or yield of the cyclohexanol of the standard, and can be appropriately selected without particular limitation, and is generally from seconds to hours. The reaction form can be either batch or continuous. The hydration reaction is generally carried out in a catalyst slurry composed of a hydrated catalyst and water, and the mixture is reacted with a mixture of cyclohexene and a mixture of cyclohexanol and an unreacted ring. The oil phase of hexene or the like is subjected to phase separation, and the oil phase is supplied to the separation step. The aqueous phase containing the catalyst is used as a catalyst slurry. It can be applied to the Chinese National Standard (CNS) A4 specification (2l〇X297 public*) according to the paper scale. (Read the first note on the back and fill in this page) •Ί Packing

1T Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 1292753 Α7 Β7 V. Invention Description (29) (Please read the note on the back and fill out this page) Ring to the reactor for reuse. The hydration reaction, in general, in addition to the cyclohexanol which produces the target product, also produces a small amount of methylcyclopentene as a by-product. The separated oil phase contains cyclohexanol, methylcyclopentene and cyclohexene, so it can be used in a conventional method such as distillation to contain a high boiling component of cyclohexanol and cyclohexene and methylcyclopentene. Wait for low boiling components to separate. The resulting cyclohexanol is separated and, if necessary, the separation method can be used to bring it to the necessary purity. At this time, the purity of cyclohexanol is preferably 99% or more. In general, the obtained unreacted cyclohexene is preferably purified to the necessary purity and recycled to the reactor for use. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, as described above, in accordance with the method of the present invention, it can be produced by simple operation and high selectivity, and can not be produced by cyclohexanone oxime. The quality of the intermediate ε-caprolactone produced has a problem in the prior art which affects the by-products which are difficult to separate and/or by-products such as ammonium sulfate having a low industrial price. In particular, in the prior art in which cyclohexanone obtained from benzene via cyclohexane is reacted with a hydroxylamine salt, the selectivity is only about 73 to 83%, and carboxylic acids, alcohols, and aldehydes are also formed. By-products such as ketones, ethers, esters, and hydrocarbons. The by-products are not the same as those of the present inventors, and since they cannot be converted into useful compounds after recycling, they are usually separated and discarded. Further, in the prior art, it is easy to generate by-products (cyclohexyl butyl ether, η-pentylcyclohexane, cyclohexyl acetic acid, hexahydrobenzaldehyde, etc.) which are not easily separated by the target product, and these by-products are liable to remain in the Cyclohexanone oxime is obtained in the transposition step of ε-caprolactam, which is known to be one of the main causes of poor quality of ε-caprolactam. However, according to the method of the present invention, the by-products are not produced. In addition, most of the by-products produced by the present invention can be reused, and the by-products that are not reused are almost all of the cyclohexane. National Standard (CNS) Α4 Specifications (210Χ297 mm) -32- 1292753 A7 B7 V. Inventions (30) (Please read the notes on the back and fill out this page) and other useful compounds, so there is very little waste. Therefore, the effect of the present invention is to use benzene as a raw material to obtain ig; (3) when using the obtained cyclohexene by the hydration reaction to obtain the cyclohexanol, the method of the present invention is used in the production of cyclohexanone oxime. This will be particularly remarkable. In this case, the method of steps (i) to (iv) is followed by recycling the by-products produced in step (iii) and/or step (iv) to the step (iii). To produce cyclohexanone | (i) a step of partially hydrogenating benzene to produce cyclohexene. (ii) a step of hydrating the obtained cyclohexene to obtain cyclohexanol. a step of aminating the cyclohexanol to produce a cyclohexylamine (iv) a step of partially cyclizing the obtained cyclohexylamine to produce cyclohexanone oxime. In each of the steps (i) to (iv), The materials, catalysts, reaction conditions and the like used in the respective steps are as described above. Specifically, in the present invention, when benzene is used as a starting material, cyclohexanone oxime has a particularly high selectivity. It has the following excellent effects: Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, printed benzene via cyclohexane In the prior art in which cyclohexanone is reacted with a hydroxylamine salt, in addition to the by-product which is not desired to be produced, a by-product of about 20 to 30% of waste is also produced in the reaction product. Further, the present invention In the method, when benzene is used as a starting material, more than 95% of the reaction product is a useful compound (cyclohexanone oxime of the target product, and cyclohexane of a useful compound), and the above does not occur. Except for undesirable by-products, most of the by-products are mostly recyclable users. In addition, when compared with the previous methods, it has a small amount of hydrogen consumption -33- This paper scale applies to Chinese national standards. (CNS) A4 specification (21〇><297 羡) 1292753 A7 _ B7 V. Description of invention (31) Advantages of cyclohexanone oxime. Therefore, the method of the present invention using benzene as a starting material is industrially The present invention is described in more detail below with reference to the embodiments and comparative examples, but the present invention is not limited thereto. Implementation It is particularly limited. Example 1 (1) Step of hydrogenating benzene to produce cyclohexene. Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, printed 5.0 g of ruthenium chloride (RuCl3-3H2〇) and 13.0 g of zinc chloride. After dissolving in 500 ml of water, stirring, and then adding 70 ml of 30% Na〇H aqueous solution, the solution was washed with 1 N NaOH. The obtained black precipitate was dispersed in 500 ml of a 5% Na〇H aqueous solution, and the inner volume was 1000 ml. After the autoclave of the mixer was attached, the total pressure was controlled to 5 MPa with hydrogen gas, and the reduction reaction was carried out at 150 ° C for 12 hours, and after washing and drying, 2.3 g of a hydrogenation catalyst was obtained. The zinc content was 7.4% by weight and the average crystal grain size was 55A. 5 g of the cerium catalyst obtained by the above treatment, 2.5 g of Zr 〇 2 powder (average particle diameter 0.3 5 / / ), zinc of basic zinc sulfate ZnS 〇 4-3 Zn (〇H) 2 was 30 mg, and 4% 280 ml of an aqueous solution of ZnS〇4 was fed into a 1000 ml autoclave made of titanium. After stirring, the mixture was heated to 150 ° C after being replaced by hydrogen, and 140 ml of benzene was further introduced thereto, and the mixture was stirred at a high pressure of 5 MPa to carry out a reaction. After 30 minutes, the reaction solution was taken out, and the composition of the oil phase was analyzed by gas chromatography. The conversion of benzene was 42.3%, and the selectivity of cyclohexene was 86.5%. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -34 - 1292753 A7 __ B7 _ V. Description of invention (32) By-product only cyclohexane (selection rate: 13.4%). Further, the analysis of the GC was carried out under the following conditions. Measuring device: GC-14A gas chromatograph analyzer (FID) of Shimadzu Corporation, Japan Column: Kabira cylinder ULB〇NHR-20M (0.25mm x 25m) manufactured by Japan Shinwa Chemical Co., Ltd. Gas: Flow rate of helium gas dissolving solution: 20ml/min Analytical method: constant temperature analysis at 50 °C The reaction mixture of the oil phase is recorded in a distillation apparatus, and extractive distillation is carried out using N,N-dimethylpropionamide as a solvent. A cyclohexene having a purity of 99.5% or more is obtained. (2) a step of hydrating cyclohexene to obtain cyclohexanol in 150 g of an aqueous solution of sulphate (Si〇2 = 29.9 wt%), adding 1 80 g of a 10% aqueous solution of tetrapropylammonium hydroxide, and then adding aluminum nitrate (A1 (N〇3) 3-9H2〇) 4g and 40g of water, stir for 1 minute. Subsequently, the solution was vigorously stirred, and concentrated nitric acid was added dropwise to prepare a gel having a pH adjusted to 10 to 10.5. This gel was fed into an autoclave equipped with a stirrer of 1000 ml of internal volume, and stirred at 180 ° C for 24 hours. The resulting product was washed with a sufficient amount of ion-exchanged water, and then dried at 10 ° C for 10 hours. This product was measured by X-ray diffraction by ZSM-5. Further, for the alumina obtained by the fluorescent X-ray analysis, the molar ratio of 矽 was 60. In addition, this product is subjected to 60 (TC) under 24 hours air circulation and the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). (Please read the back note and fill out this page) •• I installed. Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing -35-1292753 A7 B7 V. Invention description (33), ion exchange with ammonium chloride aqueous solution, and then calcined in air at 500 ° C for 4 hours In order to obtain the catalyst (please read the precautions on the back side and fill out this page). Then, in a 1000 ml autoclave with a stirrer, add 280 g of water, 30 g of cyclohexene obtained in the previous step, After 20 g of the catalyst prepared by the above method, the mixture was stirred at 100 ° C for 1 hour to carry out a reaction. After the reaction, the product was analyzed by GC, and the conversion of cyclohexene was found to be 12.4%. The selectivity of the alcohol was 99.6%. Further, the analysis of the GC was carried out under the following conditions: Measuring device: GC-14A gas chromatography analyzer (FID) of Shimadzu Corporation, Japan Column: Japan Shinwa Chemical Co., Ltd. The company's Kabila cylinder ULBON HR -20M (0. 25 mm x 25 m ) Carrier gas: Flow rate of ammonia-dissolved solution: 20 ml/min Analytical method: After 5 minutes at 50 ° C, the temperature was raised to 230 t at 10 ° C /min and held at 230 ° C for 5 minutes. The obtained reaction product is obtained by distillation to obtain a purity of 99.5% or more of the cyclohexanol Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing alcohol. (3-1) Amination of cyclohexanol to obtain cyclohexylamine -3 hydrate 47g and nickel nitrate-6 hydrate 16g dissolved in 250 ml of water to obtain an aqueous solution, add T - alumina l〇g, stir 'heated in a hot water bath to 80 ° C. Then, will dissolve A 250 ml aqueous solution containing 42 g of sodium carbonate is slowly added to the hot nickel bath in a stirred bath for 2 hours. The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -36- 1292753 A7 B7 V. (34) (Please read the precautions on the back and fill out this page) Aqueous solution. After 5 hours of aging, the resulting precipitate is filtered, washed repeatedly with warm water, and the precipitate is dried at 100 ° C for one day. One night. The dried precipitate was crushed in a mortar and fed into a quartz tube. Calcination was carried out in an electric tubular furnace at 350 ° C for 3 hours in the air to obtain a copper-nickel/r-alumina catalyst. The copper-nickel/r-alumina catalyst prepared by the above method was molded into After granules, the crucible was filled in a stainless steel tubular reactor, and hydrogen gas was introduced at a rate of 150 ml/min, and then the catalyst layer was kept at 35 (TC for 3 hours for activation treatment. After the activation treatment was completed, The temperature of the reaction gas is lowered to 18 (TC, and cyclohexanol: ammonia: hydrogen = 1: 5: 3 molar ratio of gas, under normal pressure with LSV0.1 1 / catalyst 1 / hour, so that It was reacted for 5 hours. The reaction product was analyzed by a gas chromatography analyzer to find that the conversion of cyclohexanol was 96.3%, and the selectivity of cyclohexylamine was 98.7%. The by-product was dicyclohexylamine (selectivity: 〇·8%), cyclohexylaniline (selection rate: 0.4%). Further, the analysis of the GC was carried out under the following conditions. Measuring device: GC-14A Gas Chromatography Analyzer (FID), Ministry of Economic Affairs, Ministry of Economic Affairs, Ministry of Economic Affairs, Intellectual Property Bureau, Staff Cooperatives Printed Column: Kabilla cylinder made by J&W Scientific, Germany DB-1701 (0.25mm x 30m) carrier gas: flow rate of helium gas dissolving solution: 20ml/min Analytical method: after holding at 50 ° C for 10 minutes, heat up to 300 ° C at 10 ° C / min, then After the reaction product is distilled at 300 ° C for 5 minutes, the purity of the cyclohexylamine of 99.5% or more is obtained. The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210×297 mm) -37-1292753 Α7 Β7 V. Invention Description (36) Ketone oxime. Please read the back note (3-2). The step of aminating the mixture of by-product/cyclohexanol to obtain cyclohexylamine will be carried out by the reaction of (3-1) and (3-4) above. The target product obtained from the reactants, and the following by-products obtained by distillation and separation of the unreacted materials: cyclohexanone (14.8%), nitrocyclohexane (11.2%), N-cyclohexylcyclohexylamine (47.2) %), dicyclohexylamine (21.1%) and cyclohexylaniline (11.2%) fraction 12.1g of cyclohexanol 50g were mixed, and the result of amination was carried out under the same conditions as in (3-1) above. It was found that the conversion rate was 98.5%, and the selectivity of cyclohexylamine was 97.4%. The selectivity of by-products was 2% or less in total of dicyclohexylamine and cyclohexylaniline. In Example 1, the total number of reaction steps for producing cyclohexanone from the starting material of benzene is 4 steps (partial hydrogenation of benzene, hydration of cyclohexene, amination of cyclohexanol, partial oxidation of cyclohexylamine). ). The by-product of the amination of cyclohexanol and/or partial oxidation of cyclohexylamine is recycled to the amination step. According to the selection rate of each step, the selection rate of cyclohexanone oxime based on benzene and the total carbon recovery rate of useful substances (cyclohexanone oxime, cyclohexane) are calculated according to the following calculations. Calculate the income. Selectivity of cyclohexanone oxime (%) = (formed cyclohexene moles / converted benzyl moles) X (formed cyclohexanol / converted cyclohexene) x (formed cyclohexylamine / conversion loop) Hexanol)x (Formed cyclohexanone oxime/converted cyclohexylamine molars) X 100 Full carbon recovery This paper scale applies to China National Standard (CNS) Α4 specification (210Χ297 mm) -39- 1292753 Α7 Β7 5 , invention instructions (37) (please read the precautions on the back and then fill out this page) = (generated cyclohexene moles / converted benzene moles) X (formed cyclohexanol / conversion cyclohexene) x (formed cyclohexylamine/converted cyclohexanol) x (formed cyclohexanone oxime / converted cyclohexylamine molar number) X 100+ (formation of cyclohexane molars / converted benzylol number) X 100 When cyclohexanone oxime was produced without recycling, the selectivity of cyclohexanone oxime was 74.4%, and the total carbon recovery of useful materials was 87.8% (cyclohexanone oxime: 74.4% + cyclohexane: 13.4%) . Further, when cyclohexanone oxime was obtained by recycling, the selectivity of cyclohexanone oxime was 84.8%, and the total carbon recovery of the useful substance was 98.2% (cyclohexanone oxime · 84.8% + cyclohexane: 13.4%). Further, the cyclohexanone oxime obtained in each step described above does not contain an impurity (cyclohexyl butyl ether, η- which adversely affects the quality of ε-caprolactam as an intermediate in the production of tron-6 or the like. Pentyl cyclohexane, cyclohexyl acetic acid, hexahydrobenzaldehyde, and the like. Comparative Example 1 The Cyclohexane obtained by the complete hydrogenation of benzene by the Intellectual Property Office of the Ministry of Economic Affairs of the Ministry of Economic Affairs is oxidized and dehydrogenated to obtain cyclohexanone, and is described in JP-A-58-50925. The method of synthesizing hydroxylamine sulfate, and the resulting cyclohexanone is deuterated using hydroxylamine sulfate to obtain cyclohexanone oxime. The synthesis of cyclohexanone and its deuteration are synthesized according to the following method. (1) A step of oxidizing cyclohexane by air to obtain a mixture of cyclohexanone and cyclohexanol. The paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297 mm) -40-1292753 A7 B7 V. Invention (38) In a glass autoclave having a volume of 1000 ml of a gas introduction port, 600 g of hexane and a cobalt naphthenate as a catalyst are fed at a ratio of 1 ppm (cyclohexane) to a metal atom. Into this, the oxygen-nitrogen mixed gas (capacity ratio, 〇2: N2 = 1:9) is circulated at a ratio of 1000 ml/min (NPT· conversion), and the reaction solution is stirred at 150 ° C, 1 MPa. The reaction was carried out for 40 minutes, and then the precursor gas was switched to nitrogen gas and left for 30 minutes. The reaction liquid was cooled, condensed, and refluxed to an autoclave while being exhausted, and then discarded in the atmosphere. The reaction product was analyzed by a gas chromatograph to find that the conversion of cyclohexane was 4.0%, and the selectivity of cyclohexanol and cyclohexanone was 75.8% (the formation ratio of cyclohexanol/cyclohexanone = 6/). 4). Further, the analysis method of GC is the same as the hydration reaction of the cyclohexene of Example 1 and the step (2). Further, the composition of the by-products was found to be a carboxylic acid, an aldehyde or a ketone other than cyclohexanone, an ester, an acid, an alcohol other than cyclohexanol, or a cyclohexane, as described below by GC analysis. Hydrocarbons, etc. Measuring device: GC-14A gas chromatograph analyzer (FID) of Shimadzu Corporation, Japan Column: Kabilla cylinder DB_1701 (0.25mm x 30m) manufactured by J&W Scientific, Germany Carrier gas: Ammonia gas solution flow rate: 20 ml / min Analytical method: After maintaining at 50 ° C for 10 minutes, the temperature is raised to 3 50 ° C at 10 ° C / min, and then the reaction is maintained at 35 (TC for 5 minutes). The product is subjected to alkali washing and distillation to remove unreacted cyclohexane and by-products by distillation. The yield of cyclohexanol and ring paper is applicable to the Chinese National Standard (CNS) A4 specification (210><; 297 mm) ΓPlease read the notes on the back and then fill out this page. j-Book · Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumers Cooperative Printed -41 - 1292753 A7 B7 V. Inventions (39) (Please read the back Precautions, please fill in the mixture of this product, and then distill it to distill off cyclohexanone. Then, the obtained distillation residue containing cyclohexanol is subjected to dehydrogenation reaction into a ring according to the method described later. The pentanone was then distilled to obtain cyclohexanone with a purity of 99.5%. The cyclohexanone obtained by separation and purification contains cyclohexylbutyl ether (25 00 ppm), η-pentylcyclohexane (5000 ppm), cyclohexyl acetic acid (4500 ppm), hexahydrobenzaldehyde, which are very similar to the boiling point of cyclohexanone. (200 ppm). The above-mentioned components also remain in the deuteration step described later, and in the transposition step of ε-caprolactam prepared from cyclohexanone oxime, it is known that it is mainly caused by the low quality of ε-caprolactam. Reasons: (2) Dehydrogenation of cyclohexanol to produce cyclohexanone: Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, printed in a stainless steel tubular reactor with an inner diameter of 30 mm, filled with Cu-Cr oxidation After the particulate catalyst is applied to the catalyst by a hydrogen/nitrogen mixed gas, the inlet and outlet temperatures are maintained at 265 ° C, and the cyclohexanol obtained in the previous step is pre-treated under a pressure of 0.12 MPa. Heat vaporization, and then supply LSV (liquid hourly space velocity) 0·1 1 / catalyst 1 / hour, let it react for 1 hour. The reaction liquid is recovered every hour for gas chromatographic analysis. The conversion of cyclohexanol was 71.2%, and the selectivity of cyclohexanone was 97.3. Further, the analysis method of GC is the same as the amination reaction of cyclohexanol in the step (3) of the example. The obtained reaction product is subjected to distillation to obtain cyclohexanone having a purity of 99%. (3) Ring The step of deuterated hexanone to obtain cyclohexanone oxime: In a glass mixing tank with an inner volume of 200 ml, the other paper is fed with the standard of China National Standard (CNS) A4 (210x297 public attack) ~~ " 1292753 A7 _B7 V. Invention Description (40) (Please read the note on the back and then fill out this page) Synthetic 37% by weight aqueous solution of hydroxylamine sulfate 68. lg, and keep 90 t, the previous step 14.7 g of the obtained cyclohexanone was adjusted to 5 to 7 at the pH of the reaction solution, and ammonia water was added thereto. After reacting for 30 minutes, the composition of the reaction liquid was analyzed by gas chromatography. It was found that the conversion of cyclohexanone was 95.7%, and the selectivity of cyclohexanone oxime was 99.3%. Further, the GC analysis method was the same as the amination reaction of the cyclohexanol in the step (3) of the example. After the reaction solution is allowed to stand, an by-product such as ammonium sulfate is separated by an oil phase, and the oil phase is distilled to remove cyclohexanone to obtain cyclohexanone oxime having a purity of 99.5% or more. The number of total reaction steps required for producing cyclohexanone oxime of benzene of Comparative Example 1 is 5 steps including a hydrogenation reaction of benzene and a production step of hydroxylamine. Further, the selectivity of the cyclohexanone oxime obtained in the same manner as in Example 1 was 73.2%, and a useful substance other than cyclohexanone oxime was not obtained, so that the total carbon recovery of the useful substance was 73.2%. (Generally speaking, the hydrogenation of benzene is known. The selection rate of the printing reaction of the Intellectual Property Bureau of the Intellectual Property Bureau is very high, so the selectivity of hydrogenation of benzene is assumed to be 100%). Further, among the cyclohexanone oxime obtained in each step, impurities which adversely affect the quality of the ε-caprolactam of the intermediate (cyclohexyl butyl ether, η-pentyl cyclohexane, cyclohexyl acetic acid, six) The concentration of hydrogenbenzaldehyde is almost the same as the concentration measured in the above step (1). [Industrial Applicability] According to the method of the present invention, a compound cyclohexanone oxime which is suitable as an intermediate of e-caprolactam which is a raw material such as tron-6 can be used only to make cyclohexanol and/or Cyclohexanone can be produced simply and efficiently under the starting materials. That is, according to the standard of this paper, the Chinese National Standard (CNS) A4 specification (210X297 mm) -43-1292753 Α7 Β7 5, invention description (41) The method of the invention 'is a by-product of amination and/or partial oxidation The fraction is recycled in the amination step, and the conversion of this by-product to cyclohexylamine greatly increases the selectivity of the cyclohexanone oxime of the starting material. Further, the cyclohexene obtained by hydrogenating benzene is subjected to a hydration reaction using cyclohexanol as a starting material. When the production is carried out, it is not necessary to use a base amine salt which has been subjected to a complicated step by a conventional method as a reaction reagent. Therefore, cyclohexanone oxime can be produced with a simple operation and high selectivity. In addition, according to the method of the present invention, it is not easy to produce by-products which are easily produced by the prior art and which are inferior to the quality of the compound ε-caprolactam produced by cyclohexanone oxime and/or sulfuric acid having a low industrial price. By-products such as ammonium, and most of the by-products are cyclohexanes of useful compounds, so waste is extremely rare. Therefore, according to the method of the present invention, it is extremely advantageous to manufacture a cyclohexanone oxime system in an industrial scale. This paper scale applies to China National Standard (CNS) Α4 specifications (210Χ297 mm) (please read the notes on the back and fill out this page) Printed by the Intellectual Property Office of the Ministry of Economic Affairs, Employees' Consumption Cooperatives, -5

-44

Claims (1)

1292753 Patent Application No. 9 1 1 1 6845 Patent Application Text Revision Amendment of the Republic of China February 16, 1996 Revision Bulletin ¥ 1 · A manufacturing method of cyclohexanone wins, characterized by containing (1) a benzene moiety Hydrogenation to produce cyclohexene, (2) cyclization of the obtained cyclohexene to produce cyclohexanol (3), if necessary, dehydrogenating the obtained cyclohexanol to obtain cyclohexanone Step (4) selecting the starting material selected from the group consisting of the cyclohexanol obtained in the step (2), the cyclohexanone obtained in the step (3), and a mixture thereof, and containing at least one selected from the group consisting of The elements of groups 8, 9 and 10, the amination catalyst of the elements in the group of chromium, copper, silver, zinc and aluminum, and the presence of molecular hydrogen, the step of preparing cyclohexylamine via amination reaction, Printed with the Ministry of Economic Affairs Intellectual Property Office Staff Cooperatives (5) The resulting cyclohexylamine is contained in an oxidation catalyst containing at least one element selected from the group consisting of Ti, Zr, Hf and W, or contains Si 〇. 2 gel, r -ai2o3, and can be combined with the solid catalyst required to be combined with wo3, and the molecular oxygen as an oxidant a step of producing a cyclohexanone oxime via a partial oxidation reaction in the presence of a group, wherein the by-product (α) produced in the step (4) and the by-product (/3) formed in the step (5) are grouped At least one by-product selected in the reaction system which is recycled to the amination reaction of the step (4). The paper size is applicable to the Chinese National Standard (CNS) Α4 specification (210×297 mm) A8 B8 C8 D8 1292753 6. Patent application scope 2. The method of claim 1, wherein when the cyclohexanol is used as the starting material in the step (4), the by-product (^) comprises at least one selected from the group consisting of a compound in a group of a ketone, N-(cyclohexylene)cyclohexylamine, dicyclohexylamine, cyclohexylaniline and aniline; when by using cyclohexanone as a starting material in the step (4), the by-product (α) a compound comprising at least one selected from the group consisting of cyclohexanol, N-(cyclohexylene)cyclohexylamine, dicyclohexylamine, cyclohexylaniline and aniline; and cyclohexanol in step (4) When a mixture of cyclohexanone is used as a starting material, the by-product (α) contains at least one a compound selected from the group consisting of cyclohexanol, cyclohexanone, fluorene-(cyclohexylene)cyclohexylamine, dicyclohexylamine, cyclohexylaniline, and aniline; the by-product (/3) contains at least one A compound selected from the group consisting of cyclohexanone, nitrocyclohexane, fluorene-(cyclohexylene)cyclohexylamine, and dicyclohexylamine. 3. The method of claim 1, wherein in the step (1), the benzene is partially hydrogenated, and is contained in at least one selected from the group consisting of elements belonging to Groups 8, 9 and 10 of the periodic table. The hydrogenation catalyst of the element, carried out in the presence of water. 4. The method of claim 1, wherein the partial hydrogenation reaction of the benzene is carried out in (a) a metal ruthenium having an average crystal grain size of 200 Å or less, and a hydrogenation catalyst containing a zinc compound if necessary, (b) Water, and (c) in the presence of at least one compound selected from the group consisting of zirconium or an oxide thereof, a water-soluble zinc compound, and a solid alkaline zinc sulfate, under neutral or acidic conditions, And the hydrogenation catalyst is not loaded. This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the notes on the back and fill out this page) Ordered by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperatives, Printing - 2 - 1292753 A8 B8 C8 D8 VI. Application for Patent Scope 5. For the method of claim 1, the hydration reaction of the cyclohexene is in water and Conducted as a catalyst in the presence of zeolite. 6. The method of claim 5, wherein the zeolite is selected from the group consisting of ZSM-5 zeolites. (Please read the note on the back of the department and then fill out this page) Order Printed by the Intellectual Property Office of the Ministry of Economic Affairs. The paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 3 _